CN103025821A - Heterophasic polypropylene with excellent creep performance - Google Patents

Abstract

Heterophasic propylene copolymer comprising (a) a matrix (M) being a polypropylene (PP), said polypropylene (PP) has a polydispersity index (PI) of at least 5.0, and (b) an elastomeric propylene copolymer (EC) dispersed in said matrix (M), wherein (i) said heterophasic propylene copolymer has a melt flow rate MFR2 (230 DEG C) of equal or below 1.0 g/10min, (ii) the amorphous phase (AM) of the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer has an intrinsic viscosity (IV) of at least 3.5 dl/g.

Description

Out-phase polypropylene with excellent creep property

The present invention relates to a kind of new heterophasic propylene copolymer (HECO), its manufacturing and purposes.

Heterophasic propylene copolymer is well known in the art.Such heterophasic propylene copolymer is included as the matrix of alfon or atactic propene copolymer, and elastomer copolymer is dispersed in the matrix.Thereby polypropylene-base comprises the inclusion that (meticulous) disperses, and inclusion is not the part of matrix, and described inclusion comprises elastomer copolymer.The term inclusion shows that matrix forms different phases with inclusion in heterophasic propylene copolymer, and described inclusion is for example for passing through high resolution microscopy (such as electron microscopy or scanning force microscopy (scanning force microscopy)) visible.

Use the out-phase polypropylene, it is possible producing the material with quite acceptable rigidity and impact property.Such material for example is used for the field that one side must withstand high pressure and must have on the other hand the pipe fitting of shock-resistance.

Yet present user need to realize for the specific high-performance of using and with the machinable special material of the mode with timeliness.Thereby, for example, following hope is arranged in pipe fitting industry: have and can obtain excellent rigidity and do not lose the polypropylene material that can easily process of impact property.

Therefore, the purpose of this invention is to provide a kind of polymer materials that can easily process with excellent rigidity/impact property balance that is applicable to pipe fitting industry.

Discovery of the present invention is that this material must be heterophasic propylene copolymer, and this heterophasic propylene copolymer comprises such as the polypropylene-base with wide molecular weight distribution and the elastomeric propylene multipolymer with quite high limiting viscosity.

Therefore, the present invention relates to a kind of heterophasic propylene copolymer (HECO), comprising:

(a) matrix (M), described matrix (M) are polypropylene (PP), and the polydispersity index (PI) of described polypropylene (PP) is at least 5.0;

With

(b) elastomeric propylene multipolymer (EC), described elastomeric propylene multipolymer (EC) are dispersed in the described matrix (M),

Wherein,

(i) the melt flow rate (MFR) MFR according to ISO 1133 measurements of described heterophasic propylene copolymer (HECO) ₂(230 ℃) for being equal to or less than 1.0g/10min,

(ii) amorphous phase (AM) of the cold solvend fraction of the dimethylbenzene of described heterophasic propylene copolymer (HECO) (XCS) according to ISO 1628-1 (under 135 ℃ in naphthane (decaline)) limiting viscosity (IV) measured is 3.5dl/g at least.

Preferably, polypropylene (PP) is atactic propene copolymer (R-PP) or alfon (H-PP), and alfon (H-PP) is preferred.

Unexpectedly have been found that heterophasic propylene copolymer (HECO) take in the situation that the very high rigidity of not damaging impact property as feature (referring to example).

Be described in more detail below the present invention.

Comprise as the polypropylene (PP) of matrix (M) and be dispersed in wherein elastomeric propylene multipolymer (EC) according to heterophasic propylene copolymer of the present invention (HECO).Thereby polypropylene (PP) matrix comprises the inclusion that (meticulous) disperses, and inclusion is not the part of matrix (M), and described inclusion comprises elastomeric propylene multipolymer (EC).The term inclusion shows that matrix (M) forms different phases with inclusion in heterophasic propylene copolymer (HECO), and described inclusion is for example for passing through high resolution microscopy (such as electron microscopy or scanning force microscopy) visible.

Preferably, only comprise polypropylene (PP) and elastomeric propylene multipolymer (EC) as polymeric constituent according to heterophasic propylene copolymer of the present invention (HECO).In other words, heterophasic propylene copolymer (HECO) can comprise other additive, but do not comprise other polymkeric substance, additive with based on total heterophasic propylene copolymer (HECO) surpass 5 % by weight, more preferably surpass 3 % by weight, exist such as the amount that surpasses 1 % by weight.A kind of other polymkeric substance that amount that can be low like this exists is polyethylene, and this polyethylene is the side reaction product (details is seen lower) that obtains by preparation heterophasic propylene copolymer (HECO).Therefore, especially, be understandable that the polyethylene that this heterophasic propylene copolymer (HECO) only comprises polypropylene (PP) matrix, elastomeric propylene multipolymer (EC) and randomly exists with amount mentioned in this section.

An important discovery of the present invention is that heterophasic propylene copolymer (HECO) must be take quite low melt flow rate (MFR) as feature.Melt flow rate (MFR) depends primarily on molecular-weight average.This is to make material have lower flow tendency owing to comparing long molecule with short molecule.The increase of molecular weight means reducing of MFR-value.Measure the melt flow rate (MFR) (MFR) of the polymkeric substance of under specified temp and pressure condition, discharging by the mould of regulation take g/10min as unit, and then the viscosity of polymkeric substance measured, wherein, polymkeric substance for every type, its viscosity mainly is subject to the impact of its molecular weight, also is subject to the impact of its degree of branching simultaneously.In (ISO 1133) are measured under 230 ℃ under the load of 2.16kg melt flow rate (MFR) with MFR ₂(230 ℃) expression.Therefore, preferably, in the present invention, the MFR of heterophasic propylene copolymer (HECO) ₂(230 ℃) more preferably are equal to or less than 0.8g/10min for being equal to or less than 1.0g/10min, also will be more preferably in the scope of 0.05g/10min to 1.0g/10min, more more preferably in the scope of 0.08g/10min to 0.8g/10min.

Alternatively or additionally, heterophasic propylene copolymer (HECO) is by its cross-over frequency ω _c(with the corresponding parameter of weight-average molecular weight) limits, described cross-over frequency ω _cThe storage modulus G ' and out-of-phase modulus G that in dynamic mechanical rheology test, measures " identical and be defined as handing over and get over modulus (crossover modulus) G _cFrequency.Thereby, be understandable that, heterophasic propylene copolymer (HECO) pass through dynamic rheology according to ISO 6271-10 at 200 ℃ of lower cross-over frequency ω that measure _cFor being equal to or less than 3.0rad/s, preferably being equal to or less than 2.5rad/s, as being equal to or less than 2.0rad/s.

To describe in detail as following, the matrix (M) of heterophasic propylene copolymer (HECO) is further take wide molecular weight distribution as feature.Preferably, this also is applicable to whole heterophasic propylene copolymers (HECO).Summarize as above, heterophasic propylene copolymer (HECO) need to be suitable as tube material.Thereby final heterophasic propylene copolymer (HECO) must satisfy the requirement of pipe fitting industry, yet on the other hand, final heterophasic propylene copolymer (HECO) must or can be processed economically.With in addition take wide molecular weight distribution as feature according to heterophasic propylene copolymer of the present invention (HECO), two requirements can be satisfied.Therefore, be understandable that, the dynamic rheology that passes through of heterophasic propylene copolymer (HECO) is at least 25 according to ISO 6271-10 at 200 ℃ of lower shear-thinning index SHI (3/100) that measure, more preferably at least 30, again more preferably in 25 to 100 scope, also will be more preferably 30 to 95, such as 32 to 90 scope in.

Alternatively or additionally, heterophasic propylene copolymer (HECO) is defined as 10 ⁵/ G _c(wherein, G _cFor modulus is got in the defined friendship in front) polydispersity index (PI) be at least 4.5, more preferably at least 5.0, more more preferably in 4.5 to 15.0 scope, also will be more preferably 5.0 to 11.0, such as 5.3 to 10.0 scope in.

Preferably, it is desirable for that heterophasic propylene copolymer (HECO) is thermodynamically stable.Therefore, be understandable that, the melt temperature of heterophasic propylene copolymer (HECO) is at least 158 ℃, more preferably at least 162 ℃, and also will be more preferably in 160 ℃ to 170 ℃ scope.

In addition, preferably, the Tc of heterophasic propylene copolymer (HECO) is at least 120 ℃, more preferably at least 122 ℃, and also will be more preferably in 120 ℃ to 135 ℃ scope.

Except propylene, heterophasic propylene copolymer (HECO) also comprises comonomer.Preferably, except propylene, heterophasic propylene copolymer (HECO) also comprises ethene and/or C ₄To C ₁₂Alpha-olefin.Therefore, being understood to include according to term of the present invention " propylene copolymer " can be derived from the polypropylene of following unit, preferably by forming derived from the polypropylene of following unit:

(a) propylene,

With

(b) ethene and/or C ₄To C ₁₂Alpha-olefin.

Thereby, according to propylene copolymer of the present invention (namely, heterophasic propylene copolymer (HECO), atactic propene copolymer (R-PP) and elastomeric propylene multipolymer (EC)) comprise can with the monomer of copolymerization of propylene, comonomer for example is such as ethene and/or C ₄To C ₁₂Alpha-olefin, particularly ethene and/or C ₄To C ₈Alpha-olefin, for example 1-butylene and/or 1-hexene.Preferably, propylene copolymer according to the present invention comprises following monomer, especially by following monomer composition: be selected from the group that consisted of by ethene, 1-butylene and 1-hexene can with the monomer of copolymerization of propylene.More specifically, except propylene, but propylene copolymer of the present invention also comprises the unit of derived from ethylene and/or 1-butylene.In a preferred embodiment, propylene copolymer according to the present invention comprises the only unit of derived from ethylene and propylene.Also will be more preferably, atactic propene copolymer (R-PP) (if existence) and elastomeric propylene multipolymer (EC) comprise identical comonomer, such as ethene.

Therefore, elastomeric propylene multipolymer (EC) is preferably ethylene-propylene rubber(EPR) (EPR), and polypropylene (PP) is atactic propene copolymer (R-PP) or alfon (H-PP).

In addition, be understandable that, preferably, the co-monomer content of heterophasic propylene copolymer (HECO) is in the scope of 2.0 % by weight to 14.0 % by weight, more preferably in the scope of 2.5 % by weight to 12.0 % by weight, more more preferably in the scope of 3.0 % by weight to 9.0 % by weight.

The cold solvend of dimethylbenzene (XCS) mark of measuring according to ISO6427 (23 ℃) of heterophasic propylene copolymer (HECO) is for preferably less than 15.0 % by weight, more preferably in the scope of 5.0 % by weight to 15.0 % by weight, as in the scope of 6.0 % by weight to 12.0 % by weight.

Heterophasic propylene copolymer (HECO) is limited by matrix (M) and the elastomeric propylene multipolymer (EC) that is dispersed in the matrix (M) especially.Therefore, will limit in more detail now these two kinds of components.

Matrix (M) is polypropylene (PP), more preferably is atactic propene copolymer (R-PP) or alfon (H-PP), and alfon (H-PP) is particularly preferred.

Therefore, the co-monomer content of polypropylene (PP) more preferably is no more than 0.8 % by weight again for being equal to or less than 1.0 % by weight, also will more preferably be no more than 0.5 % by weight, as is no more than 0.2 % by weight.

As mentioned above, polypropylene (PP) is preferably alfon (H-PP).

As spread all over word alfon used in the present invention and relate to basically the polypropylene that is formed by the propylene units that surpasses 99.8 % by weight.In a preferred embodiment, in alfon only propylene units can detect.Can measure co-monomer content with the FT infrared spectrometry, describe in the example part as following.

If polypropylene (PP) is atactic propene copolymer (R-PP), be understandable that so, atactic propene copolymer (R-PP) comprise can with the monomer of copolymerization of propylene, comonomer for example is such as ethene and/or C ₄To C ₁₂Alpha-olefin, particularly ethene and/or C ₄To C ₈Alpha-olefin, for example 1-butylene and/or 1-hexene.Preferably, (R-PP) comprises following monomer according to atactic propene copolymer of the present invention, especially by following monomer composition: be selected from the group that consisted of by ethene, 1-butylene and 1-hexene can with the monomer of copolymerization of propylene.More specifically, except propylene, atactic propene copolymer of the present invention (R-PP) but also comprise the unit of derived from ethylene and/or 1-butylene.In a preferred embodiment, atactic propene copolymer (R-PP) comprises the only unit of derived from ethylene and propylene.

In addition, be understandable that, preferably, the co-monomer content of atactic propene copolymer (R-PP) is within surpassing the scope of 0.2 % by weight to 1.0 % by weight, more preferably within surpassing the scope of 0.2 % by weight to 0.8 % by weight, more more preferably in the scope of 0.2 % by weight to 0.7 % by weight.

Term " random " shows that the comonomer of atactic propene copolymer (R-PP) and the first atactic propene copolymer (R-PP1), the second atactic propene copolymer (R-PP2) and the 3rd atactic propene copolymer (R-PP3) randomly is distributed in the propylene copolymer.According to IUPAC (the basic terms table in the polymer science; IUPAC recommendation 1996) understands term random.

Further, polypropylene (PP) is take wide molecular weight distribution as feature.Therefore, polypropylene (PP) is defined as 10 ⁵/ G _c(wherein, G _cFor modulus is got in the defined friendship in front) polydispersity index (PI) be at least 4.5, more preferably at least 5.0, more more preferably in 4.5 to 15.0 scope, also will be more preferably 5.0 to 12.0, such as 5.5 to 11.0 scope in.

Additionally or alternatively, the dynamic rheology that passes through of polypropylene (PP) is at least 20 according to ISO 6271-10 at 200 ℃ of lower shear-thinning index SHI (3/100) that measure, more preferably at least 25, again more preferably in 20 to 110 scope, also will be more preferably 25 to 105, such as 30 to 100 scope in.

As illustrated in above, heterophasic propylene copolymer (HECO) has quite low melt flow rate (MFR).Therefore, be equally applicable to the matrix (M) of heterophasic propylene copolymer (HECO), i.e. polypropylene (PP).Thereby, preferably, the MFR of polypropylene (PP) ₂(230 ℃) more preferably are equal to or less than 0.8g/10min for being equal to or less than 1.0g/10min, also will be more preferably in the scope of 0.05g/10min to 1.0g/10min, more more preferably in the scope of 0.08g/10min to 0.8g/10min.

Alternatively or additionally, polypropylene (PP) is limited by high molecular.Thereby, be understandable that, polypropylene (PP) pass through gel permeation chromatography (GPC; ISO 16014-4:2003) weight-average molecular weight (Mw) of measuring is 500kg/mol at least, 600kg/mol at least more preferably is more more preferably at 500kg/mol to 10, in the scope of 000kg/mol, also will be more preferably at 600kg/mol to 5, in the scope of 000kg/mol.

Further, polypropylene (PP) can be by cross-over frequency ω _cLimit.Thereby, be understandable that, polypropylene (PP) pass through dynamic rheology according to ISO 6271-10 at 200 ℃ of lower cross-over frequency ω that measure _cFor being equal to or less than 3.0rad/s, preferably be equal to or less than 2.5rad/s.

The cold solvend of dimethylbenzene (XCS) content of polypropylene (PP) is quite medium.Therefore, the cold solvend of dimethylbenzene (XCS) content of measuring according to ISO 6427 (23 ℃) is for preferably being equal to or less than 3.5 % by weight, more preferably be equal to or less than 3.0 % by weight, also will be more preferably in the scope of 0.5 % by weight to 3.5 % by weight, as in the scope of 0.5 % by weight to 3.0 % by weight.

Matrix (M), be that polypropylene (PP) can further be limited by its crystallization fraction of (SIST) measuring by segmentation isothermal isolation technique (stepwise isothermal segregation technique).The possibility that segmentation isothermal isolation technique (SIST) provides definite lamellae thickness to distribute.In the example part, describe accurate measuring method in detail.Thus, the polymer fractions of quite a large amount of at high temperature crystallizations shows that quite a large amount of sheets is brilliant.Thereby, be understandable that, polypropylene (PP) comprise at least 25.0 % by weight, more preferably at least 30.0 % by weight, more more preferably at least 35.0 % by weight, also will be more more preferably at least 40.0 % by weight have at least 24.2nm, a crystallization fraction of the lamellae thickness of 24.2nm to 84.6nm preferably, wherein determine described fraction by segmentation isothermal isolation technique (SIST).

As illustrated in above, polypropylene (PP) is take wide molecular weight distribution as feature.Preferably by three kinds of Polypropylene fractions realizations in the polypropylene (PP), described three kinds of Polypropylene fractions are different aspect weight-average molecular weight (Mw) for this wide molecular weight distribution.

Therefore, polypropylene (PP) preferably includes at least two kinds of Polypropylene fractions, more preferably comprises two or three Polypropylene fractions, more preferably is made of the melt flow rate (MFR) MFR that just measures according to ISO 1133 two or three Polypropylene fractions again ₂(230 ℃), described two or three Polypropylene fractions differs from one another.

Preferably at least a in the described Polypropylene fractions is alfon, even more preferably all (two or three) Polypropylene fractions all are homopolymer.

Thereby in a preferred embodiment, the described matrix (M) of described heterophasic propylene copolymer (HECO) (being described polypropylene (PP)) comprising:

(a) the first Polypropylene fractions (PP1), described the first Polypropylene fractions (PP1) are the first alfon (H-PP1) or the first atactic propene copolymer (R-PP1);

(b) the second Polypropylene fractions (PP2), described the second Polypropylene fractions (PP2) are the second alfon (H-PP2) or the second atactic propene copolymer (R-PP2);

(c) tripropylene fraction (PP3), described tripropylene fraction (PP3) are the 3rd alfon (H-PP3) or the 3rd atactic propene copolymer (R-PP3),

Its condition is, at least a among described three kinds of fraction PP1, PP2 and the PP3 is alfon, and preferably described at least the first Polypropylene fractions (PP1) is alfon, and more preferably all three kinds of fraction PP1, PP2 and PP3 are alfon.

Preferably, melt flow rate (MFR) MFR ₂(230 ℃) increase from the first Polypropylene fractions (PP1) to tripropylene fraction (PP3).Therefore, the melt flow rate (MFR) MFR of tripropylene fraction (PP3) ₂The melt flow rate (MFR) MFR of (230 ℃) and the first Polypropylene fractions (PP1) ₂Ratio between (230 ℃) [MFR (PP3)/MFR (PP1)] is preferably at least 20, more preferably at least 50, and/or the melt flow rate (MFR) MFR of tripropylene fraction (PP3) ₂The melt flow rate (MFR) MFR of (230 ℃) and the second Polypropylene fractions (PP2) ₂Ratio between (230 ℃) [MFR (PP3)/MFR (PP2)] is preferably at least 8, more preferably at least 12.

In another preferred embodiment, melt flow rate (MFR) MFR ₂(230 ℃) increase from the first Polypropylene fractions to the second Polypropylene fractions (PP2) and from the second Polypropylene fractions (PP2) to tripropylene fraction (PP3).Therefore, the melt flow rate (MFR) MFR of the second Polypropylene fractions (PP2) ₂(230 ℃) are than the melt flow rate (MFR) MFR of the first Polypropylene fractions (PP1) ₂(230 ℃) are higher, but than the melt flow rate (MFR) MFR of tripropylene fraction (PP3) ₂(230 ℃) are lower.

Thereby in three kinds of Polypropylene fractions PP1, PP2 and PP3, in all polymkeric substance that more preferably exist in polypropylene (PP), tripropylene fraction (PP3) has the highest melt flow rate (MFR) MFR ₂(230 ℃).

As mentioned above, particularly preferably be, at least the first Polypropylene fractions (PP1) is alfon, so-called the first alfon (H-PP1).Even more preferably, in three kinds of polypropylene PP1, PP2 and PP3, this first Polypropylene fractions (PP1) has minimum melt flow rate (MFR) MFR ₂(230 ℃).

Also will be more preferably, except the first Polypropylene fractions (PP1), the second Polypropylene fractions (PP2) or tripropylene fraction (PP3) they also are alfon.In other words, preferably, polypropylene (PP) comprises and only a kind ofly is the polypropylene of atactic propene copolymer, preferably is comprised of for the polypropylene of atactic propene copolymer a kind of.Therefore, the second Polypropylene fractions (PP2) is alfon, so-called the second alfon (H-PP2), and perhaps tripropylene fraction (PP3) is alfon, so-called the 3rd alfon (H-PP3).

Particularly preferably be, all three kinds of Polypropylene fractions PP1, PP2 and PP3 are alfon.

The below will describe three kinds of polypropylene PP1, PP2 and PP3 in more detail.

As mentioned above, polypropylene PP1, PP2 and PP3 can be atactic propene copolymer or alfon.Under any circumstance, for polypropylene PP1, PP2 and PP3, co-monomer content should be quite low.Therefore, every kind co-monomer content among three kinds of polypropylene PP1, PP2 and the PP3 more preferably is no more than 0.8 % by weight again for being no more than 1.0 % by weight, also will more preferably be no more than 0.5 % by weight.In the situation that atactic propene copolymer R-PP1, R-PP2 and R-PP3, be understandable that, every kind co-monomer content among atactic propene copolymer R-PP1, R-PP2 and the R-PP3 is within surpassing the scope of 0.2 % by weight to 1.0 % by weight, more preferably within surpassing the scope of 0.2 % by weight to 0.8 % by weight, more more preferably in the scope of 0.2 % by weight to 0.7 % by weight.

Comonomer about using in the first atactic propene copolymer (R-PP1), the second atactic propene copolymer (R-PP2) and the 3rd atactic propene copolymer (R-PP3) is referenced as the information that heterophasic propylene copolymer (HECO) provides.Therefore, R-PP1, R-PP2 and R-PP3 comprise independently of one another can with the monomer of copolymerization of propylene, comonomer for example is such as ethene and/or C ₄To C ₁₂Alpha-olefin, particularly ethene and/or C ₄To C ₈Alpha-olefin, for example 1-butylene and/or 1-hexene.Preferably, R-PP1, R-PP2 and R-PP3 comprise following monomer independently of one another, especially independently of one another by following monomer composition: be selected from the group that consisted of by ethene, 1-butylene and 1-hexene can with the monomer of copolymerization of propylene.More specifically, except propylene, but R-PP1, R-PP2 and R-PP3 also comprise the unit of derived from ethylene and/or 1-butylene independently of one another.In a preferred embodiment, except propylene, R-PP1, R-PP2 also comprise identical comonomer with R-PP3.Thereby in particularly preferred embodiment, R-PP1, R-PP2 and R-PP3 comprise the only unit of derived from ethylene and propylene.

As illustrated in above, the first polypropylene (PP1) is atactic propene copolymer (R-PP1) or alfon (H-PP1), and alfon (H-PP1) is preferred.

The cold solvend of dimethylbenzene (XCS) content of measuring according to ISO 6427 (23 ℃) of the first polypropylene (PP1) is for preferably being equal to or less than 5.0 % by weight, more preferably be equal to or less than 4.5 % by weight, also will be more preferably in the scope of 0.8 % by weight to 4.5 % by weight, as in the scope of 0.8 % by weight to 3.0 % by weight.

As illustrated in above, the first polypropylene (PP1) is with quite low melt flow rate (MFR) MFR ₂(230 ℃) are feature.Therefore, be understandable that, according to the melt flow rate (MFR) MFR of ISO 1133 measurements ₂(230 ℃) preferably are no more than 0.07g/10min for being no more than 0.1g/10min, also will be more preferably in the scope of 0.001g/10min to 0.1g/10min, more more preferably in the scope of 0.004g/10min to 0.07g/10min.

Alternatively or additionally, the first polypropylene (PP1) is limited by high molecular.Thereby, be understandable that, the first polypropylene (PP1) pass through gel permeation chromatography (GPC; ISO 16014-4:2003) weight-average molecular weight (Mw) of measuring is at least 2,000kg/mol, more preferably at least 5,000kg/mol, more more preferably 2,000kg/mol to 50, in the scope of 000kg/mol, also will be more preferably 5,000kg/mol to 20 is in the scope of 000kg/mol.

The second polypropylene (PP2) can be atactic propene copolymer (the second atactic propene copolymer (R-PP2)) or alfon (the second alfon (H-PP2)), and alfon (the second alfon (H-PP2)) is preferred.

The cold solvend of dimethylbenzene (XCS) content of measuring according to ISO 6427 (23 ℃) of the second polypropylene (PP2) is for preferably being equal to or less than 4.0 % by weight, more preferably be equal to or less than 3.5 % by weight, also will more preferably be equal to or less than 3.0 % by weight.

As illustrated in above, the melt flow rate (MFR) MFR of the second polypropylene (PP2) ₂(230 ℃) are than the melt flow rate (MFR) MFR of tripropylene (PP3) ₂(230 ℃) are lower.On the other hand, the melt flow rate (MFR) MFR of the first polypropylene (PP1) ₂(230 ℃) can be than the melt flow rate (MFR) MFR of the second polypropylene (PP2) ₂(230 ℃) lower or with the melt flow rate (MFR) MFR of the second polypropylene (PP2) ₂(230 ℃) are identical, preferably than the melt flow rate (MFR) MFR of the second polypropylene (PP2) ₂(230 ℃) are lower.Therefore, be understandable that the melt flow rate (MFR) MFR according to ISO 1133 measurements of the second polypropylene (PP2) ₂(230 ℃) are in the scope of 0.005g/10min to 2.0g/10min, preferably in the scope of 0.008g/10min to 1.5g/10min, as in the scope of 0.008g/10min to 1.0g/10min.

Alternatively or additionally, the second polypropylene (PP2) is limited by high molecular.Thereby, be understandable that, the second polypropylene (PP2) pass through gel permeation chromatography (GPC; ISO 16014-4:2003) weight-average molecular weight (Mw) of measuring is 500kg/mol at least, 800kg/mol at least more preferably is more more preferably at 500kg/mol to 4, in the scope of 000kg/mol, also will be more preferably at 750kg/mol to 3, in the scope of 500kg/mol.

Preferably, described the first polypropylene (PP1) is 82: 18 to 25: 75 with the weight ratio of described the second polypropylene (PP2), more preferably 80: 20 to 30: 70.

Tripropylene (PP3) can be atactic propene copolymer (the 3rd atactic propene copolymer (R-PP3)) or alfon (the 3rd alfon (H-PP3)), and alfon (the 3rd alfon (H-PP3)) is preferred.

The cold solvend of dimethylbenzene (XCS) content of measuring according to ISO 6427 (23 ℃) of tripropylene (PP3) is for preferably being equal to or less than 4.5 % by weight, more preferably be equal to or less than 3.5 % by weight, also will be more preferably less than 2.5 % by weight.

As illustrated in above, preferably in three kinds of polypropylene PP1, PP2 and PP3, tripropylene (PP3) has the highest melt flow rate (MFR) MFR ₂(230 ℃), in the polymkeric substance that more preferably exists in polypropylene (PP), tripropylene (PP3) has the highest melt flow rate (MFR) MFR ₂(230 ℃).Therefore, be understandable that the melt flow rate (MFR) MFR according to ISO 1133 measurements of tripropylene (PP3) ₂(230 ℃) are 4.0g/10min at least, and 8.0g/10min at least more preferably is more more preferably in the scope of 4.0g/10min to 100g/10min.

Alternatively or additionally, tripropylene (PP3) is limited by its weight-average molecular weight (Mw).Thereby, be understandable that, tripropylene (PP3) pass through gel permeation chromatography (GPC; ISO 16014-4:2003) weight-average molecular weight (Mw) of measuring more preferably is no more than 700kg/mol, more more preferably in the scope of 100kg/mol to 800kg/mol for being no more than 800kg/mol.

Very good result is attainable, if described polypropylene (PP) comprising:

(a) 15.0 % by weight to 35.0 % by weight, described first polypropylene (PP1) of 16.0 % by weight to 32.0 % by weight preferably,

(b) 29.0 % by weight to 48.0 % by weight, described second polypropylene (PP2) of 31.0 % by weight to 45.0 % by weight preferably, and

(c) 18.0 % by weight to 55.0 % by weight, the described tripropylene (PP3) of 20.0 % by weight to 51.0 % by weight preferably,

Total amount based on described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3).

Preferably, prepare polypropylene (PP) with sequential polymerization processes, preferably as described in detail below.Therefore, three kinds of polypropylene PP1, PP2 and PP3 are homogenizing mixture, can not obtain homogenizing mixture by mechanical blending.

Another important component of heterophasic propylene copolymer (HECO) is for being dispersed in the elastomeric propylene multipolymer (EC) in the matrix (being polypropylene (PP)).Comonomer about using in the elastomeric propylene multipolymer (EC) is referenced as the information that heterophasic propylene copolymer (HECO) provides.Therefore, elastomeric propylene multipolymer (EC) comprise can with the monomer of copolymerization of propylene, comonomer for example is such as ethene and/or C ₄To C ₁₂Alpha-olefin, particularly ethene and/or C ₄To C ₈Alpha-olefin, for example 1-butylene and/or 1-hexene.Preferably, elastomeric propylene multipolymer (EC) comprises following monomer, especially by following monomer composition: be selected from the group that consisted of by ethene, 1-butylene and 1-hexene can with the monomer of copolymerization of propylene.More specifically, except propylene, elastomeric propylene multipolymer (EC) but also comprise the unit of derived from ethylene and/or 1-butylene.Thereby in particularly preferred embodiment, elastomeric propylene multipolymer (EC) comprises the only unit of derived from ethylene and propylene.

The cold solvend of dimethylbenzene (XCS) content of the heterophasic propylene copolymer (HECO) that the character major effect of elastomeric propylene multipolymer (EC) is final and amorphous phase (AM).Thereby according to the present invention, the amorphous phase (AM) of heterophasic propylene copolymer (HECO) is considered to the elastomeric propylene multipolymer (EC) of heterophasic propylene copolymer (HECO).

Therefore, an important requirement of the present invention is that elastomeric propylene multipolymer (EC) has quite high weight-average molecular weight.The high weight-average molecular weight of high inherent viscosity (IV) value reflection.Thereby, be understandable that, the limiting viscosity (IV) of measuring according to ISO 1628-1 (under 135 ℃ in naphthane) of the amorphous phase (AM) of the cold solvend fraction of the dimethylbenzene of heterophasic propylene copolymer (HECO) (XCS) is 3.5dl/g at least, 4.0dl/g at least more preferably, also will be more preferably in the scope of 3.5dl/g to 6.0dl/g, as in the scope of 3.8dl/g to 5.0dl/g.

Co-monomer content in the elastomeric propylene multipolymer (EC), preferably ethylene content is relatively low.Therefore, in a preferred embodiment, the co-monomer content of the amorphous phase (AM) of the cold solvend fraction of the dimethylbenzene of heterophasic propylene copolymer (HECO) (XCS), more preferably ethylene content is less than 40.0 % by weight, more preferably less than 37.0 % by weight, more more preferably in 25.0 % by weight to 40.0 % by weight, scope such as 30.0 % by weight to 38.0 % by weight.

Preferably, heterophasic propylene copolymer according to the present invention (HECO) comprising:

(a) 80.0 % by weight to 94.0 % by weight, the described polypropylene (PP) of 83.0 % by weight to 94.0 % by weight more preferably, and

(b) 6.0 % by weight to 20.0 % by weight, the described elastomer copolymer (EC) of 6.0 % by weight to 17.0 % by weight more preferably,

Based on the total amount of described polypropylene (PP) and described elastomer copolymer (EC), wherein, the amount of the amorphous phase of the amount of described elastomer copolymer (EC) and the cold solvend of dimethylbenzene (XCS) fraction part (AM) is corresponding.

At last, heterophasic propylene copolymer of the present invention (HECO) is classified feature below preferably as:

(i) at least 1400MPa, the tensile modulus of measuring according to ISO 527-2 of 1600MPa at least more preferably, and/or

(ii) 30kJ/m at least ², 45kJ/m at least preferably ²According to ISO 179 (1eA; 23 ℃) the Sha Erpi notched Izod impact strength measured.

Can comprise the nearly additive (such as nucleator and antioxidant) of 2.0 % by weight such as the heterophasic propylene copolymer (HECO) defined in the present invention, and slip(ping)agent.

The invention still further relates to heterophasic propylene copolymer (HECO) is used for pipe fitting (as without penstock spare) or is used for the parts of pipe fitting (as without penstock spare) and for the manufacture of the purposes of pipe fitting.In addition, the present invention relates to heterophasic propylene copolymer (HECO) and be used for sheet material, section bar and the accessory purposes of (as being used for the accessory without penstock spare).

In addition, the present invention relates to sheet material, section bar, accessory and pipe fitting, such as the pipe fitting accessory, particularly without penstock spare, described sheet material, section bar, accessory and pipe fitting comprise such as the heterophasic propylene copolymer (HECO) defined in the present invention, preferably include at least 75 % by weight such as the heterophasic propylene copolymer (HECO) defined in the present invention, more preferably comprise at least 90 % by weight, as at least 95 % by weight such as the heterophasic propylene copolymer (HECO) defined in the present invention, most preferably formed by the heterophasic propylene copolymer defined in the present invention (HECO).

As used herein, term " pipe fitting " is intended to comprise that length is greater than the hollow bodY of diameter.And term " pipe fitting " should also comprise additional parts, as accessory, valve and need to be used for for example all parts of indoor soil and refuse tube system or underground sewage pipe fitting system.

Pipe fitting according to the present invention comprises monoblock type pipe fitting (solid wall pipe) and structural walls pipe fitting (structured wall pipe).The monoblock type pipe fitting can be individual layer pipe fitting or multilayer pipe fitting.Yet preferably, the monoblock type pipe fitting is the individual layer pipe fitting.The structural walls pipe fitting preferably is comprised of two-layer, and wherein one deck is level and smooth internal layer, and another layer is skin ripple, spiral winding or barring.More preferably, composition of the present invention be included in such structural walls pipe fitting the layer at least one deck in.

Be used for to comprise common subsidiary material according to the heterophasic propylene copolymer (HECO) of pipe fitting of the present invention, for example, nearly weighting agent and/or the stablizer of 0.01 % by weight to 2.5 % by weight and/or processing aid and/or the static inhibitor of 0.1 % by weight to 1.0 % by weight and/or the toughener (for example glass fibre) of 0.2 % by weight to 3.0 % by weight of 0.01 % by weight to 10 % by weight of 10 % by weight are in each case based on employed heterophasic propylene copolymer (HECO) (% by weight that provides in this section refers to comprise the total amount of pipe fitting and/or the pipe fitting layer of described heterophasic propylene copolymer (HECO)).

Preferably, by preparing as the above heterophasic propylene copolymer that limits (HECO) such as the following sequential polymerization processes that limits.

Therefore, the present invention relates to a kind of sequential polymerization processes for the preparation of heterophasic propylene copolymer according to the present invention (HECO), described heterophasic propylene copolymer (HECO) comprises the first polypropylene (PP1), the second polypropylene (PP2) and tripropylene (PP3), wherein, said method comprising the steps of:

(a1) make propylene and at least a ethene and/or at least a C randomly ₄To C ₁₂Alpha-olefin is at the first reactor

(R1) polymerization in obtains the first polypropylene (PP1), and preferably described the first polypropylene (PP1) is the first alfon (H-PP1);

(b1) described the first polypropylene (PP1) is transferred in the second reactor (R2);

(c1) in described the second reactor (R2) and in the presence of described the first polypropylene (PP1), make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing obtains the second polypropylene (PP2) thus, and preferably described the second polypropylene (PP2) is the second alfon (H-PP2), and described the first polypropylene (PP1) mixes with described the second polypropylene (PP2);

(d1) mixture of step (c1) is transferred in the 3rd reactor (R3);

(e1) in described the 3rd reactor (R3) and the described mixture that in step (c1), obtains in the presence of make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing, obtain thus tripropylene (PP3), preferably described tripropylene (PP3) is the 3rd alfon (H-PP3), and described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3) form described polypropylene (PP);

(f1) described polypropylene (PP) is transferred in the 4th reactor (R4); With

(g1) in described the 4th reactor (R4) and in the presence of described polypropylene (PP), make propylene and at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing obtains elastomeric propylene multipolymer (EC) thus, and described polypropylene (PP) and described elastomeric propylene multipolymer (EC) form described heterophasic propylene copolymer (HECO); Perhaps

(a2) make propylene and at least a ethene and/or C ₄To C ₂₀Alpha-olefin polymerization in the first reactor (R1) obtains the second polypropylene (PP2), and preferably described the second polypropylene (PP2) is the second alfon (H-PP2);

(b2) described the second polypropylene (PP2) is transferred in the second reactor (R2);

(c2) in described the second reactor (R2) and in the presence of described the second polypropylene (PP2), make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing, obtain thus tripropylene (PP3), preferably described tripropylene (PP3) is the 3rd alfon (H-PP3), and described the second polypropylene (PP2) mixes with described the 3rd alfon (H-PP3);

(d2) mixture of step (c2) is transferred in the 3rd reactor (R3);

(e2) in described the 3rd reactor (R3) and the described mixture that in step (c2), obtains in the presence of make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing, obtain thus the first polypropylene (PP1), preferably described the first polypropylene (PP1) is the first alfon (H-PP1), and described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3) form described polypropylene (PP);

(f2) described polypropylene (PP) is transferred in the 4th reactor (R4); With

(g2) in described the 4th reactor (R4) and in the presence of described polypropylene (PP), make propylene and at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing obtains elastomeric propylene multipolymer (EC) thus, and described polypropylene (PP) and described elastomeric propylene multipolymer (EC) form described heterophasic propylene copolymer (HECO).

Preferably, between described the second reactor (R2) and described the 3rd reactor (R3), and randomly between described the 3rd reactor (R3) and described the 4th reactor (R4), monomer is flashed out.

For the preferred embodiment of heterophasic propylene copolymer (HECO), polypropylene (PP), the first polypropylene (PP1), the second polypropylene (PP2) and tripropylene (PP3) and elastomeric propylene multipolymer (EC), with reference to above given definition.

Term " sequential polymerization processes " is illustrated in the described polypropylene of preparation in the reactor of at least four series connection.Therefore, the present invention comprises the first reactor (R1), the second reactor (R2), the 3rd reactor (R3) and the 4th reactor (R4) at least.Term " polymerization reactor " should represent that main polyreaction occurs.Thereby if the method is comprised of four polymerization reactors, following selection is not got rid of in this definition: total method comprises for example prepolymerization step in pre-polymerization reactor.Term " by ... form " only be the closed statement aspect main polymerization reactor.

Preferably described the first reactor (R1) is slurry reactor (SR), and can be in body or slurry, operate any continuously or the tank reactor or circulating reactor at intermittence of simple agitation.Body refers to the polyreaction in the reaction medium of the monomer that comprises at least 60% (w/w).According to the present invention, preferably, described slurry reactor (SR) is (body) circulating reactor (LR).

Preferably, described the second reactor (R2), the 3rd reactor (R3) and the 4th reactor (R4) are Gas-phase reactor (GPR).Such Gas-phase reactor (GPR) can be any mechanically stirred reactor or fluidized-bed reactor.Preferably, described Gas-phase reactor (GPR) comprises having at least churned mechanically fluidized-bed reactor of the gas velocity of 0.2m/sec.Thereby, being understandable that, described Gas-phase reactor is the fluidized-bed reactor that preferably has mechanical stirrer.

Thereby, in a preferred embodiment, described the first reactor (R1) is slurry reactor (SR), such as circulating reactor (LR), and described the second reactor (R2), the 3rd reactor (R3) and the 4th reactor (R4) are Gas-phase reactor (GPR).Therefore, for present method, use at least four polymerization reactors, four polymerization reactors preferably, i.e. slurry reactor (SR) (such as circulating reactor (LR)), the first Gas-phase reactor (GPR-1), the second Gas-phase reactor (GPR-2) and the 3rd Gas-phase reactor (GPR-3) of series connection.If necessary, at described slurry reactor (SR) before, place pre-polymerization reactor.

Preferred multi-stage process is " circulation (loop)-gas phase " method, such as by Borealis A/S, " circulation-gas phase " method that for example (such as in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315) describes in patent documentation of Denmark exploitation (is called as BORSTAR

Technology).

Further suitable slurry-gas phase process is the Spheripol of Basell Method.

Preferably, as the above method for the preparation of atactic propene copolymer (R-PP) that limits in, described first reactor (R1) of step (a), i.e. described slurry reactor (SR), such as circulating reactor (LR), condition can be as follows:

-temperature be in 50 ℃ to 110 ℃ scope, preferably in the scope between 60 ℃ and 100 ℃, in 68 ℃ to 95 ℃ scope,

-pressure is in the scope of 20 bar to 80 bar, preferably in the scope between 40 bar to 70 cling to,

-can add hydrogen, be used for controlling in a manner known way molar mass.

Subsequently, will transfer to described the second reactor (R2) from the reaction mixture of step (a), namely Gas-phase reactor (GPR-1) namely arrives step (c), thereby preferably the condition in step (c) is as follows:

-temperature is in 50 ℃ to 130 ℃ scope, preferably in the scope between 60 ℃ and 100 ℃,

-pressure is in the scope of 5 bar to 50 bar, preferably in the scope between 15 bar to 35 cling to,

-can add hydrogen, be used for controlling in a manner known way molar mass.

In described the 3rd reactor (R3) and described the 4th reactor (R4), preferably the condition in described the second Gas-phase reactor (GPR-2) and described the 3rd Gas-phase reactor (GPR-4) is similar with condition in described the second reactor (R2).

In three reactor zones, the residence time can change.

In an embodiment for the preparation of described polyacrylic method, the residence time in bulk reaction device, for example circulating reactor be 0.1 hour to 2.5 hours, for example in 0.15 hour to 1.5 hours the scope, and the residence time in Gas-phase reactor generally can for 0.2 hour to 6.0 hours, such as 0.5 hour to 4.0 hours.

If wish, polyreaction can be in known manner at described the first reactor (R1), be to realize under the super critical condition in the described slurry reactor (SR) (as described circulating reactor (LR)) and/or as the condensation mode in described Gas-phase reactor (GPR).

Preferably, described method also comprises the prepolymerization with catalyst system, describes in detail as following, and this catalyst system comprises Z-N Primary Catalysts (procatalyst), external donor and promotor randomly.

In a preferred embodiment, prepolymerization is as the reaction of body slurry polymerisation in liquid propene and carry out, and namely liquid phase mainly comprises propylene, wherein other reactants of small amount and randomly inert component be dissolved in the propylene.

Typically, prepolymerization is at 10 ℃ to 60 ℃, preferably 15 ℃ to 50 ℃ and more preferably carry out under 20 ℃ to 45 ℃ the temperature.

Pressure in pre-polymerization reactor is not critical, but must be sufficiently high, so that reaction mixture is remained in the liquid phase.Thereby pressure can be 20 bar to 100 bar, for example 30 bar to 70 bar.

Preferably, catalyst component is all introduced prepolymerization step.Yet in the situation that ingredient of solid catalyst (i) and individually charging of promotor (ii), possible is, only some promotor is introduced prepolymerisation stage, and the remainder of promotor is introduced subsequently polymerization stage.Equally, under these circumstances, be necessary that, so many promotor is introduced prepolymerisation stage, so that obtain therein sufficient polyreaction.

It is possible that other components are also added prepolymerisation stage.Thereby, hydrogen can be added prepolymerisation stage, to control as known in the art the molecular weight of prepolymer.Further, can use anti static additive, be attached to each other or be attached to the wall of reactor to prevent particle.

Accurate control to prepolymerization condition and reaction parameter is in the technology of this area.

According to the present invention, described heterophasic propylene copolymer (HECO) is by multistage polymerization process, as described above, in the presence of catalyst system and obtain, catalyst system comprises that the Z-N Primary Catalysts comprises the product of transesterification reaction of lower alcohol and phthalic acid ester as the Z-N Primary Catalysts of component (i).

Prepare by following steps according to Primary Catalysts used in the present invention:

A) make MgCl ₂And C ₁-C ₂The spray crystallization of alcohol or the emulsion adducts and the TiCl that solidify ₄Reaction;

B) make the stage a) product and the bialkyl ortho phthalate of formula (I) at described C ₁To C ₂Alcohol and the transesterification reaction between the bialkyl ortho phthalate of described formula (I) occur to form in to reacting under the condition of body,

Wherein, R ^{1 '}And R ^{2 '}At least one C independently ₅Alkyl;

C) product washing stage b); Perhaps

D) randomly make step c) product and other TiCl ₄Reaction.

As for example defined in patent application WO 87/07620, WO 92/19653, WO 92/19658 and the EP 0 491 566, the preparation Primary Catalysts.The content of these files is included in herein by reference.

At first, form MgCl ₂With formula MgCl ₂* the C of nROH ₁-C ₂The adducts of alcohol, wherein R is methyl or ethyl, and n is 1 to 6.Preferably, use ethanol as alcohol.

Use adducts as support of the catalyst, then adducts at first is melted and is solidified by spray crystallization or emulsion.

In next step, make formula MgCl ₂* the adducts and the TiCl that solidify of the spray crystallization of nROH or emulsion ₄Contact, to form the carrier of titanizing, wherein R is methyl or ethyl, preferably ethyl, and n is 1 to 6, then is following steps:

● in the carrier of described titanizing, add

(i) bialkyl ortho phthalate of formula (I), wherein R ^{1 '}And R ^{2 '}At least one C independently ₅Alkyl is such as at least one C ₈Alkyl,

Or preferably,

(ii) bialkyl ortho phthalate of formula (I), wherein R ^{1 '}And R ^{2 '}Be identical, and be at least one C ₅Alkyl is such as at least one C ₈Alkyl,

Or more preferably,

(iii) be selected from by the own ester of phthalic acid propyl group (PrHP), dioctyl phthalate (DOP) (DOP), the bialkyl ortho phthalate of the formula (I) of the group that two (tridecyl) esters (DTDP) of Di Iso Decyl Phthalate (DIDP) and phthalic acid consist of, more preferably the bialkyl ortho phthalate of formula (I) is dioctyl phthalate (DOP) (DOP) again, such as dimixo-octyl phthalate or phthalic acid two (ethylhexyl) (diethylhexylphthalate), phthalic acid two (ethylhexyl) particularly

To form the first product;

● make described the first product stand suitable transesterification reaction condition, namely greater than 100 ℃, preferably between 100 ℃ to 150 ℃, the temperature between 130 ℃ to 150 ℃ more preferably, so that the described ester group of the bialkyl ortho phthalate of described methyl alcohol or ethanol and described formula (I) carries out transesterify, to form preferably at least 80 % by mole, more preferably 90 % by mole, the bialkyl ortho phthalate of 95 % by mole formula (II) most preferably

Wherein, R ¹And R ²Methyl or ethyl, ethyl preferably,

The bialkyl ortho phthalate of described formula (II) is interior to body; With

● reclaim the described product of transesterification reaction as primary catalyst component (component (i)).

In a preferred embodiment, make formula MgCl ₂* the adducts of nROH fusing, wherein R is methyl or ethyl, and n is 1 to 6, then preferably, with gas melts the is injected solvent be cooled or the gas that is cooled, thereby make described adducts crystallize into form favourable on the morphology, as for example described in the WO 87/07620.

Preferably, use the adducts of this crystallization as support of the catalyst, and make the adducts reaction of this crystallization, to form useful Primary Catalysts among the present invention, described at WO 92/19658 and WO 92/19653.

Because remove relict catalyst by extraction, so obtain carrier and the interior adducts to body of titanizing, wherein changed by ester alcohol (ester alcohol) derivative group.

If enough titaniums are stayed on the described carrier, so enough titaniums will be as the active element of Primary Catalysts.

Otherwise, after above processing, repeat titanizing, in order to guarantee enough titanium concentration, thereby guarantee activity.

Preferably, comprise the at the most titanium of 2.5 % by weight according to Primary Catalysts used in the present invention, the titanium of 2.2% % by weight at the most preferably, and the titanium of 2.0 % by weight at the most more preferably.Primary Catalysts to body burden for preferably between 4 % by weight to 12 % by weight, and more preferably between 6 % by weight and 10 % by weight.

More preferably, by using ethanol as alcohol and using dioctyl phthalate (DOP) (DOP) to prepare according to Primary Catalysts used in the present invention as the bialkyl ortho phthalate of formula (I), produce the diethyl phthalate (DEP) as interior donor compound.

Also will be more preferably, be that the BC-1 catalyzer of Borealis is (such as disclosed catalyzer according to WO 92/19653 preparation in WO 99/24479 according to Primary Catalysts used in the present invention; Use dioctyl phthalate (DOP) as the bialkyl ortho phthalate of formula (I) according to WO 92/19658 especially) or from the commercially available catalyst P olytrack 8502 of Grace.

In order to prepare according to heterophasic propylene copolymer of the present invention (HECO), employed catalyst system preferably includes, except special-purpose Z-N Primary Catalysts, as the organo-metallic promotor of component (ii).

Therefore, preferably, this promotor is selected from the group that is made of trialkylaluminium (such as triethyl aluminum (TEA)), dialkylaluminum chloride and alkyl sesquialter aluminum chloride (alkyl aluminium sesquichloride).

The component of employed catalyst system (iii) is the external donor by formula (III) expression:

Si(OCH ₃) ₂R ₂ ⁵ (III)

Wherein, R ⁵Representative has the branched-chain alkyl of 3 to 12 carbon atoms, preferably has the branched-chain alkyl of 3 to 6 carbon atoms, perhaps has the cycloalkyl of 4 to 12 carbon atoms, preferably has a cycloalkyl of 5 to 8 carbon atoms.

Particularly preferably be R ⁵Be selected from the group that is consisted of by sec.-propyl, isobutyl-, isopentyl, the tertiary butyl, tert-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and suberyl.

More preferably, external donor is selected from by diethylin triethoxyl silane [Si (OCH ₂CH ₃) ₃(N (CH ₂CH ₃) ₂)], dicyclopentyl dimethoxyl silane [Si (OCH ₃) ₂(cyclopentyl) ₂], diisopropyl dimethoxy silane [Si (OCH ₃) ₂(CH (CH ₃) ₂) ₂] and composition thereof the group that consists of.

In a further embodiment, can carry out modification to the Z-N Primary Catalysts by in the presence of catalyst system, making the vinyl compound polymerization, this catalyst system comprises special-purpose Z-N Primary Catalysts (component (i)), external donor (component (ii)) and promotor (component (iii)) randomly, and this vinyl compound has following formula:

CH ₂＝CH-CHR ³R ⁴

Wherein, R ³And R ⁴Form together five yuan or hexa-atomic saturated, undersaturated or aromatic ring or independently representative comprise the alkyl of 1 to 4 carbon atom, and the catalyzer that is modified is for the preparation of heterophasic propylene copolymer according to the present invention.The vinyl compound that is aggregated can be used as α-nucleator.

About the modification of catalyzer, with reference to International Application No. WO 99/24478, WO 99/24479 and WO 00/68315 especially, incorporate by reference this paper into about the reaction conditions of the modification of catalyzer and about polymer reaction.

Then, heterophasic propylene copolymer (HECO) as described in will adding such as the additive as illustrated in above is collected described heterophasic propylene copolymer (HECO) from the final reactor of reactor series.Preferably, in a step distribution, before extruding operation or in extruding the operation process, these additives are mixed into composition.Alternatively, can prepare masterbatch, wherein said heterophasic propylene copolymer (HECO) at first only mixes with in the described additive some.

In order to mix, can use conventional batching or blending equipment, Banbury mixing machine for example, 2-roller rubber grinding machine, Buss-co-kneader (Buss-co-kneader) or twin screw extruder.The polymer materials that reclaims from forcing machine is in pellet form usually.Then preferably, for example, by injection molding these pellets are further processed, to produce the article of heterophasic propylene copolymer of the present invention (HECO), such as pipe fitting.

Use various batchings known and commonly used and in the blend method any in resin batching field can make according to heterophasic propylene copolymer of the present invention (HECO) micronize and mixing.

Further specify the present invention below by example.

Example

A. measuring method

Following term definition and measuring method are applicable to above-mentioned general description of the present invention and following example, unless otherwise defined.

The calculating of the co-monomer content of described the second polypropylene (PP2):

$\frac{C\left(R2\right)-w\left(\mathrm{PP}1\right)\mathrm{xC}\left(\mathrm{PP}1\right)}{w\left(\mathrm{PP}2\right)}=C\left(\mathrm{PP}2\right)---\left(I\right)$

Wherein,

W (PP1) is described the first polypropylene (PP1), is the weight fraction of the product of described the first reactor (R1),

W (PP2) is described the second polypropylene (PP2), be the weight fraction of the polymkeric substance of preparation in described the second reactor (R2),

C (PP1) is described the first polypropylene (PP1), be described the first reactor (R1) product pass through the co-monomer content [take % by weight as unit] that Fourier transform infrared spectroscopy art (FTIR) is measured,

C (R2) is the product that obtains in described the second reactor (R2), be described the first polypropylene (PP1) and described the second polypropylene (PP2) mixture pass through the co-monomer content [take % by weight as unit] that Fourier transform infrared spectroscopy art (FTIR) is measured

C (PP2) is calculated co-monomer content [take % by weight as unit] of described the second polypropylene (PP2).

The calculating of the cold solvend of dimethylbenzene (XCS) content of described the second polypropylene (PP2):

$\frac{\mathrm{XS}\left(R2\right)-w\left(\mathrm{PP}1\right)\mathrm{xXS}\left(\mathrm{PP}1\right)}{w\left(\mathrm{PP}2\right)}=\mathrm{XS}\left(\mathrm{PP}2\right)---\left(\mathrm{II}\right)$

Wherein,

W (PP1) is described the first polypropylene (PP1), is the weight fraction of the product of described the first reactor (R1),

W (PP2) is described the second polypropylene (PP2), be the weight fraction of the polymkeric substance of preparation in described the second reactor (R2),

XS (PP1) is described the first polypropylene (PP1), be described the first reactor (R1) product according to ISO 6427 at the 23 ℃ of lower cold solvend of dimethylbenzene (XCS) content [take % by weight as unit] of measuring,

XS (R2) is the product that obtains in described the second reactor (R2), be described the first polypropylene (PP1) and described the second polypropylene (PP2) mixture according to ISO 6427 at the 23 ℃ of lower cold solvend of dimethylbenzene (XCS) content [take % by weight as unit] of measuring

XS (PP2) is the cold solvend of calculated dimethylbenzene (XCS) content [take % by weight as unit] of described the second polypropylene (PP2).

The melt flow rate (MFR) MFR of described the second polypropylene (PP2) ₂The calculating of (230 ℃):

$\mathrm{MFR}\left(\mathrm{PP}2\right)={10}^{\left[\frac{\log \left(\mathrm{MFR}\left(R2\right)\right)-w\left(\mathrm{PP}1\right)x\log \left(\mathrm{MFR}\left(\mathrm{PP}1\right)\right)}{w\left(\mathrm{PP}2\right)}\right]}---\left(I\right)$

Wherein,

W (PP1) is described the first polypropylene (PP1), is the weight fraction of the product of described the first reactor (R1),

W (PP2) is described the second polypropylene (PP2), be the weight fraction of the polymkeric substance of preparation in described the second reactor (R2),

MFR (PP1) is described the first polypropylene (PP1), is the melt flow rate (MFR) MFR according to ISO 1133 measurements of the product of described the first reactor (R1) ₂(230 ℃) [take g/10min as unit],

MFR (R2) is the product that obtains in described the second reactor (R2), be the melt flow rate (MFR) MFR that measures according to ISO 1133 of the mixture of described the first polypropylene (PP1) and described the second polypropylene (PP2) ₂(230 ℃) [take g/10min as unit],

MFR (PP2) is calculated melt flow rate (MFR) MFR of described the second polypropylene (PP2) ₂(230 ℃) [take g/10min as unit].

The calculating of the co-monomer content of described tripropylene (PP3):

$\frac{C\left(R3\right)-w\left(R2\right)\mathrm{xC}\left(R2\right)}{w\left(\mathrm{PP}3\right)}=C\left(\mathrm{PP}3\right)---\left(\mathrm{IV}\right)$

Wherein,

W (R2) is described the second reactor (R2), is the weight fraction of the mixture of described the first polypropylene (PP1) and described the second polypropylene (PP2),

W (PP3) is described tripropylene (PP3), be the weight fraction of the polymkeric substance of preparation in described the 3rd reactor (R3),

C (R2) be described the second reactor (R2) product, be described the first polypropylene (PP1) and described the second polypropylene (PP2) mixture pass through the co-monomer content [take % by weight as unit] that Fourier transform infrared spectroscopy art (FTIR) is measured

C (R3) is the product that obtains in described the 3rd reactor (R3), be described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3) mixture pass through the co-monomer content [take % by weight as unit] that Fourier transform infrared spectroscopy art (FTIR) is measured

C (PP3) is calculated co-monomer content [take % by weight as unit] of described tripropylene (PP3).

The calculating of the cold solvend of dimethylbenzene (XCS) content of described tripropylene (PP3):

$\frac{\mathrm{XS}\left(R3\right)-w\left(R2\right)\mathrm{xXS}\left(R2\right)}{w\left(\mathrm{PP}3\right)}=\mathrm{XS}\left(\mathrm{PP}3\right)---\left(V\right)$

Wherein,

W (R2) is described the second reactor (R2), is the weight fraction of the mixture of described the first polypropylene (PP1) and described the second polypropylene (PP2),

W (PP3) is described tripropylene (PP3), be the weight fraction of the polymkeric substance of preparation in described the 3rd reactor (R3),

XS (R2) be described the second reactor (R2) product, be described the first polypropylene (PP1) and described the second polypropylene (PP2) mixture according to ISO 6427 at the 23 ℃ of lower cold solvend of dimethylbenzene (XCS) content [take % by weight as unit] of measuring

XS (R3) is the product that obtains in described the 3rd reactor (R3), be described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3) mixture according to ISO 6427 at the 23 ℃ of lower cold solvend of dimethylbenzene (XCS) content [take % by weight as unit] of measuring

XS (PP3) is the cold solvend of calculated dimethylbenzene (XCS) content [take % by weight as unit] of described tripropylene (PP3).

The melt flow rate (MFR) MFR of described tripropylene (PP3) ₂The calculating of (230 ℃):

$\mathrm{MFR}\left(\mathrm{PP}3\right)={10}^{\left[\frac{\log \left(\mathrm{MFR}\left(R3\right)\right)-w\left(R2\right)x\log \left(\mathrm{MFR}\left(R2\right)\right)}{w\left(\mathrm{PP}3\right)}\right]}---\left(\mathrm{II}\right)$

Wherein,

W (R2) is described the second reactor (R2), is the weight fraction of the mixture of described the first polypropylene (PP1) and described the second polypropylene (PP2),

W (PP3) is described tripropylene (PP3), be the weight fraction of the polymkeric substance of preparation in described the 3rd reactor (R3),

MFR (R2) be described the second reactor (R2) product, be the melt flow rate (MFR) MFR that measures according to ISO 1133 of the mixture of described the first polypropylene (PP1) and described the second polypropylene (PP2) ₂(230 ℃) [take g/10min as unit],

MFR (R3) is the product that obtains in described the 3rd reactor (R3), be the melt flow rate (MFR) MFR that measures according to ISO 1133 of the mixture of described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3) ₂(230 ℃) [take g/10min as unit],

MFR (PP3) is calculated melt flow rate (MFR) MFR of described tripropylene (PP3) ₂(230 ℃) [take g/10min as unit].

The NMR-spectroscopy measurements

Polyacrylic from the sample record that is dissolved in 1,2,4-trichlorobenzene/benzene-d6 (90/10 w/w) under 130 ℃ on Bruker 400MHz spectrograph ¹³C-NMR spectrum.For five element analysises, according to document: (T.Hayashi, Y.Inoue, R.

And T.Asakura, Polymer 29 138-43 (1988); And Chujo R, etc., Polymer 35 339 (1994)) in the method described and belong to (assignment).

Use NMR to measure and be used for determining mmmm five unit concentration in mode as known in the art.

Degree of randomness

In FTIR measures, with thickness be the film of 250mm at 225 ℃ of lower compression moldings, and be the film of 250mm at the 2000FTIR of Perkin-Elmer system instrument research thickness.Use ethene peak area (760cm ^-1-700cm ^-1) as the tolerance of total ethylene content.Absorption band for structure-P-E-P-(ethylene unit between propylene units) appears at 733cm ^-1The place.These bands of a spectrum represent the feature of random ethylene content.For long ethene sequence (surpassing two unit), absorption band appears at 720cm ^-1The place.Usually, for random copolymers, observe and the corresponding shoulder of long ethene batch (run).By ¹³C-NMR carries out based on area to the calibration of total ethylene content with based at 733cm ^-1The peak height at place is to the calibration of random ethylene (PEP) content.(Thermochimica Acta，66(1990)53-68)。

Number-average molecular weight (M _n), weight-average molecular weight (M _w) and molecular weight distribution (MWD) by gel permeation chromatography (GPC) determined according to following methods:

Measure weight-average molecular weight Mw and molecular weight distribution (MWD=Mw/Mn, wherein Mn is number-average molecular weight, and Mw is weight-average molecular weight) by the method based on ISO 16014-1:2003 and ISO 16014-4:2003.Use is equipped with Waters Alliance GPCV 2000 instruments of refractive index detector and in-line viscometer, under 145 ℃ and under the constant flow rate at 1mL/min, use the 3x tsk gel post (GMHXL-HT) from TosoHaas, and with 1,2,4-trichlorobenzene (TCB, by 2 of 200mg/L, 6-di-t-butyl-4-methyl-phenol is stable) is as solvent.The each analysis injected 216.5 μ L sample solutions.Use in the scope of 0.5kg/mol to 11500kg/mol 19 narrow MWD polystyrene (PS) standards and the relative calibration of the wide polypropylene standard of one group of well-characterized calibrate the post group.By the polymer dissolution of 5mg-10mg is kept shaking continuously preparing all samples in 3 hours by stable TCB (identical with moving phase) and before sampling is in the GPC instrument at 10mL (under 160 ℃).

Rheology:

Under nitrogen atmosphere, carrying out the dynamic rheology measurement at 200 ℃ of lower diameters that use as plate and the plate geometries (plate geometry) of 25mm with Rheometrics RDA-II QC on the sample of compression molding.Shake shearing experiment under the frequency at 0.01rad/s to 500rad/s in the linear viscoelasticity scope of strain.(ISO 6721-10)

Storage modulus (G '), out-of-phase modulus (G "), complex modulus (G ^*) and complex viscosity (η ^*) value as the function of frequency (ω) and obtain.

The complex flow (complex fluidity) that use is defined as the inverse of complex viscosity calculates zero-shear viscosity (η ₀).Thereby its real part and imaginary part are limited by following formula:

F ' (ω)=η ' (ω)/[η ' (ω) ²+ η " (ω) ²] and

f”(ω)＝η”(ω)/[η′(ω) ²+η”(ω) ²]

From following equation:

η '=G "/ω and η "=G '/ω

f′(ω)＝G”(ω)*ω/[G′(ω) ²+G”(ω) ²]

f”(ω)＝G′(ω)*ω/[G′(ω) ²+G”(ω) ²]

Polydispersity index, PI,

PI=10 ⁵/ Gc, from G ' (ω) and G " (ω) intersection point calculation, for its G ' (ω c)=G " (ω c)=Gc is suitable for.

Shear-thinning index SHI is according to Heino ^1,2)(following) and calculate, shear-thinning index SHI is relevant with MWD and do not rely on Mw.SHI (3/100) is defined in the ratio of complex viscosity and complex viscosity under the shear-stress of 200 ℃ and 100kPa (η * 100) under the shear-stress of 200 ℃ and 3kPa (η * 3).

1)Rheological characterization of polyethylene fractions.Heino，E.L.；Lehtinen，A；Tanner，J.； J.Neste Oy，Porvoo，Finland.Theor.Appl.Rheol.，Proc.Int.Congr.Rheol.，11 ^th(1992)，1360-362

2)The influence of molecular structure on some rheological properties of polyethylene.Heino，Eeva-Leena.Borealis Polymers Oy，Porvoo，Finland.Annual Transactions of the Nordic Rheology Society，1995

Cross-over frequency ω c

Cross-over frequency ω c from G ' (ω) and G " (ω) intersection point determines, for its G ' (ω c)=G " (ω c)=Gc is suitable for.

Melt flow rate (MFR) (MFR ₂)

With 2.16kg (MFR ₂) load 230 ℃ of lower melt flow rate (MFR)s of measuring.Melt flow rate (MFR) is the amount that is normalized to the polymkeric substance in grams that the testing installation of ISO1133 extruded in 10 minutes under the load at 2.16kg under 230 ℃ the temperature.

Co-monomer content

By being calibrated to from quantitatively ¹³The result's that C NMR spectroscopic analysis obtains quantitative Fourier transform infrared spectroscopy art (FTIR) is measured the co-monomer content of multipolymer.

At the thickness that under 190 ℃ film is pressed onto between 300 μ m to 500 μ m, and with transmission mode film is carried out the spectrum record.Relevant instrument setting comprises 5000 to 400 wave number (cm ^-1) the spectrum window, 2.0cm ^-1Resolving power and 8 times scanning.

Use is at 767cm ^-1Peak maximum after the baseline correction of the quantitative bands of a spectrum at place is determined the butene content of propene-1-butene copolymer, and wherein baseline is from 780cm ^-1-750cm ^-1Limit.

Use is at 727cm ^-1Peak maximum after the baseline correction of the quantitative bands of a spectrum at place is determined the hexene content of propylene-hexene copolymer, and wherein baseline is from 758.5cm ^-1To 703.0cm ^-1Limit.

Use the film thickness method to use the intensity I (q) of quantitative bands of a spectrum and the thickness T of the film of being pressed is used following relation: [I (q)/T] m+c=C determines co-monomer content C, wherein m and c be from use from ¹³The coefficient that the working curve that the co-monomer content that C NMR spectroscopic analysis obtains is constructed is determined.

The cold solvend fraction of dimethylbenzene (XCS % by weight)

Under 23 ℃, measure the cold solvend fraction of dimethylbenzene (XCS) according to ISO 6427.

Amorphous content (AM) is by separating the cold solvend fraction of above dimethylbenzene (XCS) and making the amorphous phase partly precipitated and measured with acetone.With throw out filtration and lower dry at 90 ℃ in vacuum furnace.

$\mathrm{AM}\%=\frac{100\mathrm{xm}1\mathrm{xv}0}{m0\mathrm{xv}1}$

Wherein,

" AM% " is the amorphous phase mark,

" m0 " is initial polymer amount (g),

" m1 " is sedimentary weight (g),

" v0 " is original volume (ml),

" v1 " is the volume (ml) of analyzed sample.

Melt temperature T _m, Tc T _cMeasured on the sample of 5mg to 10mg with Mettler TA820 dsc (DSC).Obtain crystallization curve and melting curve in 10 ℃/min cooling between 30 ℃ and 225 ℃ and the heating scanning process.The peak value of melt temperature and Tc being regarded as endothermic curve and exotherm.

Equally, measure fusion enthalpy and crystallization enthalpy (Hm and Hc) by the DSC method according to ISO 11357-3.

Segmentation isothermal isolation technique (SIST)

The isothermal crystal that is used for the SIST analysis is carrying out under the temperature that reduces gradually between 200 ℃ and 105 ℃ on the sample of Mettler TA820 DSC at 3 ± 0.5mg.

(i) make sample at 225 ℃ of lower fusing 5min,

(ii) then be cooled to 145 ℃ with 80 ℃/min,

(iii) 145 ℃ of lower maintenances 2 hours,

(iv) then be cooled to 135 ℃ with 80 ℃/min,

(v) 135 ℃ of lower maintenances 2 hours,

(vi) then be cooled to 125 ℃ with 80 ℃/min,

(vii) 125 ℃ of lower maintenances 2 hours,

(viii) then be cooled to 115 ℃ with 80 ℃/min,

(ix) 115 ℃ of lower maintenances 2 hours,

(x) then be cooled to 105 ℃ with 80 ℃/min,

(xi) 105 ℃ of lower maintenances 2 hours.

In the end after the step, make sample be cooled to-10 ℃ with 80 ℃/min, and by with the heating rate of 10 ℃/min with the sample heating that is cooled until 200 ℃ obtain melting curve.All measurements are all carried out in nitrogen atmosphere.Fusion enthalpy is recorded as the function of temperature and by measuring at 50 ℃ to 60 ℃; 60 ℃ to 70 ℃; 70 ℃ to 80 ℃; 80 ℃ to 90 ℃; 90 ℃ to 100 ℃; 100 ℃ to 110 ℃; 110 ℃ to 120 ℃; 120 ℃ to 130 ℃; 130 ℃ to 140 ℃; 140 ℃ to 150 ℃; 150 ℃ to 160 ℃; 160 ℃ to 170 ℃; 170 ℃ to 180 ℃; 180 ℃ to 190 ℃; The fusion enthalpy of the fraction that melts in 190 ℃ to 200 ℃ the temperature interval and estimated.

Can use the melting curve of the material of by this way crystallization to be used for calculating the lamellae thickness distribution according to Thomson-Gibbs equation (Eq 1.):

$T_m=T_0(1-\frac{2\mathrm{\σ}}{\mathrm{\Δ}{H}_0\·L})---\left(1\right)$

Wherein, T ₀=457K, Δ H ₀=134x10 ⁶J/m ³, σ=49.6x10 ^-3J/m ³, and L is lamellae thickness.

Tensile modulus is according to ISO 527-2 (pinblock speed (cross head speed)=50mm/min; 23 ℃) use such as the injection molding sample of describing among the EN ISO 1873-2 (dog bone shape, thickness are 4mm) and measure.

The Sha Erpi notched Izod impact strength is measured by the injection molding test samples of describing in using such as EN ISO 1873-2 (80x10x4mm) under 23 ℃, 0 ℃ and-20 ℃ according to ISO 179/1eA.

B. example

All polymkeric substance all are produced in the Borstar pilot plant with pre-polymerization reactor, a slurry reactor and three Gas-phase reactor.According to ratio listed in the table 1, from the commercially available catalyst P olytrack of Grace (US) 8502 and diethylin triethoxyl silane [Si (OCH as external donor ₂CH ₃) ₃(N (CH ₂CH ₃) ₂)] and be combined with as the triethyl aluminum (TEAL) of activator and trapping agent.In table 1 for circulating reactor pointed " dynamically hydrogen feed " by with pulse duration of 5min hydrogen pulsing being fed to pre-polymerization reactor with timed interval of 30min, cause in circulating reactor effectively H2/C3 than between 25mol/mol and 110mol/mol, being the variation of the sawtooth function of 30min according to the time.

Table 1: the preparation of heterophasic propylene copolymer (HECO)

Parameter	Unit	IE 1	IE 2	CE 1	CE 2
						Pre-polymerization reactor
Temperature	[℃]	35	35	35	35
						Pressure	[kPa]	5100	5200	5100	5200
Al/ is to the body ratio	[moles/mole]	4	4	4	4
						The residence time	[h]	0.3	0.3	0.3	0.3
Circulating reactor
						Temperature	[℃]	85	85	70	70
Pressure	[kPa]	5500	5400	5400	5400
						The residence time	[h]	0.14	0.17	0.2	0.3
Ethylene feed	[kg/h]	0	0	2	2.3
						The H2/C3 ratio	[mole/kilomol]	Dynamic H 2Charging	Dynamic H 2Charging	Dynamic H 2Charging	Dynamic H 2Charging
GPR 1
						Temperature	[℃]	80	80	80	80
Pressure	[kPa]	2100	2100	2100	2250
						The residence time	[h]	2.2	2.3	2.2	2.1
Ethylene feed	[kg/h]	0	0	0	0
						The H2/C3 ratio	[mole/kilomol]	49	3.1	3.4	5.5
The C2/C3 ratio	[mole/kilomol]	0	0	8.3	8.9
						GPR 2
Temperature	[℃]	85	85	85	85
						Pressure	[kPa]	3200	3200	3200	3200
The residence time	[h]	2.9	2.6	2.5	2.6
						Ethylene feed	[kg/h]	0.13	0.11	0.07	0.08
The H2/C3 ratio	[moles/mole]	0.03	71	60	77
						The C2/C3 ratio	[mole/kilomol]	0	0	0	0
GPR 3
						Temperature	[℃]	70	75	75	75
Pressure	[kPa]	2100	2200	2200	2200
						The residence time	[h]	0.7	0.9	0.6	0.8
Ethylene feed	[kg/h]	27	27	27	27
						The H2/C2 ratio	[mole/kilomol]	21	22	21	19
The C2/C3 ratio	[mole/kilomol]	538	550	568	545

Table 2: the character of the heterophasic propylene copolymer of circulating reactor, GPR1, GPR2 (HECO)

Table 3: the character of heterophasic propylene copolymer (HECO); GPR3, matrix (circulating reactor, GPR1, GPR2), final

		IE 1	IE 2	CE 1	CE 2
						GPR3
Division		9.3	6.4	7.9	8.5
						IV(AM)	[dl/g]	4.2	4	4.2	4.7
C2(AM)	[% by weight]	32.9	34.6	34.5	33.4
						The C2 of GPR3	[% by weight]	3.9	3.3	5	5.2
Final XS	[% by weight]	11.4	9.8	11.7	12.3
						Final AM	[% by weight]	10.7	9.1	10.9	10.8
Final MFR	[g/10min]	0.34	0.42	0.32	0.23
						Matrix
MFR 2	[g/10min]	0.5	0.6	0.5	0.4
						Tm	[℃]	169	168	162	161
Tc	[℃]	128	128	125	125
						Tensile modulus	[MPa]	2224	2254	1783	1700
Mn	[kg/mol]	88	86	92	80
						Mw	[kg/mol]	643	628	637	844
ω c	[rad/s]	0.9	2	1.4	0.7
						PI	-	7.9	6.2	6.4	7.9
SHI(3/100)	-	85	53	56	84
						All
ω c	[rad/s]	0.57	1.8	1.0	0.65
						PI	-	8.3	5.5	5.9	6.5
SHI(3/100)	-	95	40	46	60
						Tm	[℃]	168	169	162	161
Tc	[℃]	129	129	125	125
						Tensile modulus	[MPa]	1790	1900	1420	1400
NIS(23℃)	[kJ/m 2]	61	50	17.8	48.3
						NIS(0℃)	[kJ/m 2]	10	8.2	6	6.1
NIS(-20℃)	[kJ/m 2]	5.9	5.4	6	6.1

Table 3:SIST character

		IE 1	IE 2	CE 1	CE 2
						The T scope	The Lc scope	Mark	Mark	Mark	Mark
[℃]	[nm]	[% by weight]	[% by weight]	[% by weight]	[% by weight]
						50-60	2.52-2.73	0.0	0.1	0.2	0.1
60-70	2.74-2.97	0.0	0.2	0.0	0.4
						70-80	2.98-3.25	0.0	0.3	0.4	0.7
80-90	3.26-3.60	0.0	0.3	0.7	1.1
						90-100	3.61-4.03	0.0	0.3	0.8	1.4
100-110	4.04-4.57	0.0	0.3	0.8	1.4
						110-120	4.58-5.28	0.2	0.4	1.7	2.3
120-130	5.29-6.26	0.6	0.8	3.4	4.3
						130-140	6.27-7.69	1.6	1.6	5.6	7.1
140-150	7.70-9.95	4.0	3.9	9.9	11.5
						150-160	9.96-14.09	13.0	12.7	19.7	21.2
160-170	14.09-24.16	37.0	36.2	41.7	40.2
						170-180	24.16-84.55	42.9	42.1	15.2	8.3
＞180	＞84.55	0.8	0.7	0.0	0.0

Claims (17)

1. a heterophasic propylene copolymer (HECO) comprising:

(a) matrix (M), described matrix (M) are polypropylene (PP), and the polydispersity index (PI) of described polypropylene (PP) is at least 5.0;

With

(b) elastomeric propylene multipolymer (EC), described elastomeric propylene multipolymer (EC) are dispersed in the described matrix (M),

Wherein,

(i) the melt flow rate (MFR) MFR according to ISO 1133 measurements of described heterophasic propylene copolymer (HECO) ₂(230 ℃) for being equal to or less than 1.0g/10min,

(ii) limiting viscosity (IV) of measuring according to ISO 1628-1 (under 135 ℃ in naphthane) of the amorphous phase (AM) of the cold solvend fraction of the dimethylbenzene of described heterophasic propylene copolymer (HECO) (XCS) is 3.5dl/g at least.

2. heterophasic propylene copolymer according to claim 1 (HECO), wherein, described heterophasic propylene copolymer (HECO) has:

(i) at least 4.5 polydispersity index (PI),

And/or

(ii) at least 25.0 the shear-thinning index SHI (3/100) according to ISO 6271-10 (200 ℃) measurement,

And/or

(iii) be equal to or less than the cross-over frequency ω that measures according to ISO 6271-10 (200 ℃) of 3.0rad/s _c

3. heterophasic propylene copolymer according to claim 1 and 2 (HECO), wherein, described heterophasic propylene copolymer (HECO) has:

(i) co-monomer content in the scope of 2.0 % by weight to 14.0 % by weight,

And/or

(ii) co-monomer content in the amorphous phase in the scope of 25.0 % by weight to 40.0 % by weight (AM),

And/or

(iii) less than the cold solvend of dimethylbenzene (XCS) mark of measuring according to ISO6427 (23 ℃) of 15.0 % by weight.

4. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim, wherein, described heterophasic propylene copolymer (HECO) has:

(i) at least 158 ℃ melt temperature Tm,

And/or

(ii) at least 120 ℃ Tc Tc,

And/or

(iii) 30kJ/m at least ²According to ISO 179 (1eA; 23 ℃) the Sha Erpi notched Izod impact strength measured,

And/or

(iv) tensile modulus of measuring according to ISO 527-2 of 1400MPa at least.

5. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim, wherein, described polypropylene (PP) has:

(i) be equal to or less than the melt flow rate (MFR) MFR that measures according to ISO 1133 of 1.0g/10min ₂(230 ℃), and/or

(ii) be equal to or less than the co-monomer content of 1.0 % by weight,

And/or

(iii) at least 20.0 the shear-thinning index SHI (3/100) according to ISO 6271-10 (200 ℃) measurement,

And/or

(iv) be equal to or less than the cold solvend of dimethylbenzene (XCS) mark of measuring according to ISO6427 (23 ℃) of 3.5 % by weight.

6. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim, wherein, described polypropylene (PP) comprises at least three kinds of Polypropylene fractions, the melt flow rate (MFR) MFR that just measures according to ISO 1133 ₂(230 ℃), described three kinds of Polypropylene fractions differ from one another, and preferably at least a in described three kinds of polypropylene is alfon, is homopolymer or multipolymer and remain two kinds of polypropylene.

7. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim, wherein, described polypropylene (PP) comprising:

(a) the first polypropylene (PP1), described the first polypropylene (PP1) are the first alfon (H-PP1) or the first atactic propene copolymer (R-PP1);

(b) the second polypropylene (PP2), described the second polypropylene (PP2) are the second alfon (H-PP2) or the second atactic propene copolymer (R-PP2);

(c) tripropylene (PP3), described tripropylene (PP3) are the 3rd alfon (H-PP3) or the 3rd atactic propene copolymer (R-PP3),

Its condition is, at least a among described three kinds of polypropylene PP1, PP2 and the PP3 is alfon,

Wherein further,

(i) in described three kinds of polypropylene PP1, PP2 and PP3, described the first polypropylene (PP1) has the minimum melt flow rate (MFR) MFR according to ISO 1133 measurements ₂(230 ℃),

And/or

(ii) described three kinds of polypropylene PP1, PP2 and PP3 are at the melt flow rate (MFR) MFR that measures according to ISO 1133 ₂(230 ℃) aspect is different.

8. heterophasic propylene copolymer according to claim 7 (HECO), wherein, described the first polypropylene (PP1) that is preferably the first alfon (H-PP1) has:

(i) be no more than the melt flow rate (MFR) MFR that measures according to ISO 1133 of 0.1g/10min ₂(230 ℃),

And/or

(ii) be no more than the co-monomer content of 2.5 % by weight,

And/or

(iii) be equal to or less than the cold solvend of dimethylbenzene (XCS) mark of measuring according to ISO6427 (23 ℃) of 5.0 % by weight.

9. according to claim 7 or 8 described heterophasic propylene copolymers (HECO), wherein,

(i) be preferably the melt flow rate (MFR) MFR that measures according to ISO 1133 of described second polypropylene (PP2) of the second alfon (H-PP2) ₂(230 ℃) are in the scope of 0.005g/10min to 2.0g/10min,

And/or

(ii) be preferably the melt flow rate (MFR) MFR that measures according to ISO 1133 of the described tripropylene (PP3) of the 3rd alfon (H-PP3) ₂(230 ℃) are 4.0g/10min at least.

10. each described heterophasic propylene copolymer (HECO) in 9 according to claim 7, wherein, described the first polypropylene (PP1) is 80: 20 to 25: 75 with the weight ratio of described the second polypropylene (PP2).

11. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim, wherein, the comonomer of described elastomer copolymer (EC) is ethene and/or at least a C ₄To C ₁₀Alpha-olefin.

12. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim, wherein, the co-monomer content of the amorphous phase (AM) of the cold solvend fraction of the dimethylbenzene of described heterophasic propylene copolymer (HECO) (XCS) is less than 40.0 % by weight.

13. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim, wherein, described heterophasic propylene copolymer (HECO) comprising:

(a) the described polypropylene (PP) of 80.0 % by weight to 94.0 % by weight, and

(b) the described elastomer copolymer (EC) of 6.0 % by weight to 20.0 % by weight,

Total amount based on described polypropylene (PP) and described elastomer copolymer (EC).

14. according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim 7 to 14, wherein, described polypropylene (PP) comprising:

(a) described first polypropylene (PP1) of 15.0 % by weight to 35.0 % by weight,

(b) described second polypropylene (PP2) of 29.0 % by weight to 48.0 % by weight, and

(c) the described tripropylene (PP3) of 18.0 % by weight to 55.0 % by weight,

Total amount based on described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3).

15. one kind is used for the method for sequential polymerization processes preparation according to each described heterophasic propylene copolymer (HECO) of aforementioned claim, described heterophasic propylene copolymer (HECO) comprises the first polypropylene (PP1), the second polypropylene (PP2) and tripropylene (PP3), wherein, said method comprising the steps of:

(a1) make propylene and at least a ethene and/or at least a C randomly ₄To C ₁₂Alpha-olefin polymerization in the first reactor (R1) obtains the first polypropylene (PP1), and preferably described the first polypropylene (PP1) is the first alfon (H-PP1);

(b1) described the first polypropylene (PP1) is transferred in the second reactor (R2);

(c1) in described the second reactor (R2) and in the presence of described the first polypropylene (PP1), make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing obtains the second polypropylene (PP2) thus, and preferably described the second polypropylene (PP2) is the second alfon (H-PP2), and described the first polypropylene (PP1) mixes with described the second polypropylene (PP2);

(d1) mixture of step (c1) is transferred in the 3rd reactor (R3);

(e1) in described the 3rd reactor (R3) and the described mixture that in step (c1), obtains in the presence of make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing, obtain thus tripropylene (PP3), preferably described tripropylene (PP3) is the 3rd alfon (H-PP3), and described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3) form described polypropylene (PP);

(f1) described polypropylene (PP) is transferred in the 4th reactor (R4); With

(g1) in described the 4th reactor (R4) and in the presence of described polypropylene (PP), make propylene and at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing obtains elastomeric propylene multipolymer (EC) thus, and described polypropylene (PP) and described elastomeric propylene multipolymer (EC) form described heterophasic propylene copolymer (HECO);

Perhaps

(a2) make propylene and at least a ethene and/or C ₄To C ₂₀Alpha-olefin polymerization in the first reactor (R1) obtains the second polypropylene (PP2), and preferably described the second polypropylene (PP2) is the second alfon (H-PP2);

(b2) described the second polypropylene (PP2) is transferred in the second reactor (R2);

(c2) in described the second reactor (R2) and in the presence of described the second polypropylene (PP2), make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing, obtain thus tripropylene (PP3), preferably described tripropylene (PP3) is the 3rd alfon (H-PP3), and described the second polypropylene (PP2) mixes with described the 3rd alfon (H-PP3);

(d2) mixture of step (c2) is transferred in the 3rd reactor (R3);

(e2) in described the 3rd reactor (R3) and the described mixture that in step (c2), obtains in the presence of make propylene and randomly at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing, obtain thus the first polypropylene (PP1), preferably described the first polypropylene (PP1) is the first alfon (H-PP1), and described the first polypropylene (PP1), described the second polypropylene (PP2) and described tripropylene (PP3) form described polypropylene (PP);

(f2) described polypropylene (PP) is transferred in the 4th reactor (R4); With

(g2) in described the 4th reactor (R4) and in the presence of described polypropylene (PP), make propylene and at least a ethene and/or C ₄To C ₁₂Alpha-olefine polymerizing obtains elastomeric propylene multipolymer (EC) thus, and described polypropylene (PP) and described elastomeric propylene multipolymer (EC) form described heterophasic propylene copolymer (HECO).

16. according to the purposes of each described heterophasic propylene copolymer (HECO) in pipe fitting in the aforementioned claim 1 to 14.

17. a pipe fitting, described pipe fitting comprise according to each the described heterophasic propylene copolymer (HECO) in the aforementioned claim 1 to 14.